This invention relates to functional resins derived from polyamines and a process for producing the same.
Many reports on the synthesis of functional resins having carbon-carbon unsaturated bonding portions at side chains of polymers can be divided into the following two categories.
One of them includes a process wherein a vinyl compound having an allyl group (CH.sub.2 .dbd.CHCH.sub.2 --), which is poor in polymerizability, in its molecule is synthesized and only a vinyl group is selectively polymerized to yield a functional resin having unsaturated groups at side chains; or a process wherein a compound having a functional group (e.g. an epoxy group) which is capable of ring opening polymerization, and a vinyl group and only the ring portion is subjected to ring opening polymerization to yield a functional resin.
The other of them includes a process wherein a suitable resin is selected as a support, which is reacted with a compound having a suitably modified carbon-carbon unsaturated bonding portion to yield a functional resin.
Examples of the former category are syntheses of functional resins having unsaturated groups at side chains by subjecting, for example, acrylic acid (or methacrylic acid) allyl ester, vinyl ethylene oxide, or methacrylic acid glycidyl ester to anion polymerization for polymerizing only the ethylene oxide rings selectively [e.g. M. Dorati, et al: Makromol. Chem. vol. 60, pp. 233-235 (1963); G. Allen, et al: Polymer vol. 5, pp. 553-557 (1964); T. Otsu, et al: Makromol. Chem. vol. 71, pp. 150-158 (1964)]. But these processes are not suitable for industrially practical syntheses of functional resins, since various problems arise in that side reactions such as partial polymerization occur during monomer synthesis, which results in making the separation and purification of the monomer difficult. In the case of applying the functional resins to a special use, the unsaturated groups which are active portions become too active to use. Ionic polymerization is a relatively difficult polymerization technique; and during the polymerization, some unsaturated groups which should be retained as they are as unreacted portions at side chains participate in the polymerization to cause a crosslinking reaction, which results in making the produced resin insoluble.
Examples of the latter category are functional resins obtained by reacting polyvinyl alcohol with cinnamic acid chloride. Such resins are available commercially as photosensitive resins but have a defect in that the development by using neutral water is difficult.
The latter functional resins are usually coated on a glass or metal plate, and exposed to light or heat as an energy source to crosslink unsaturated groups at side chains among polymers to give an insolubilized coating film. When the resin is applied to such a utility, the resin should be not only good in film-forming properties and flexibility but also good in adhesiveness to glass, wooden plate and metal. But the above-mentioned functional resins are not always sufficient as to adhesiveness.
On the other hand, in order to enhance the reactivity of functional resins having functional groups at side chains, it is necessary to facilitate the association between a reactive portion and a substance to be reacted. For such a purpose, it is desirable that the main chain portion is flexible, and the side chain portion is long to some extent and flexible so as to be bent freely. In other words, the main chain portion is preferably a support having no rigid ring portions and no hetero atoms such as a sulfur atom and an oxygen atom. Further, in order to show good adhesiveness to glass, wood, metal and the like material, these functional resins should have functional groups which show large affinity to these materials at side chains. Production of such functional resins satisfying the above-mentioned requirements has not been reported yet.